Study on the efficiency and mechanism of iron-modified cyanobacteria biochar in removing tetracycline from water
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摘要:
以蓝藻为原料制备生物炭，通过考察不同温度制备的蓝藻生物炭对四环素的吸附效能，筛选最优制备温度。采用液相还原法制备不同铁炭比的铁改性蓝藻生物炭，研究其对四环素的去除效能、影响因素及去除机理。结果表明：在700 ℃、铁炭质量比为1∶1条件下制备的铁改性蓝藻生物炭对四环素具有高效去除能力，60 min去除率可达87.2%，为改性前的1.2倍，吸附类型符合伪二级动力学方程（R2>0.99）。通过傅里叶红外光谱、扫描电镜、X射线光电子能谱、X射线衍射探讨铁改性蓝藻生物炭去除四环素性能与其结构的关系。结果表明，铁改性蓝藻生物炭对四环素的去除机理主要为吸附和化学降解作用，零价铁作为电子供体促进氧化还原反应的发生，含氧官能团作为电子转移桥梁在吸附降解过程中起着重要作用。影响因素试验结果表明，阴离子对铁改性蓝藻生物炭去除水中四环素效能的影响程度为SO4 2−>Cl−，阳离子影响程度为Ca2+>Na+，有机质黄腐酸相对于离子强度影响程度较弱。铁改性蓝藻生物炭对四环素类抗生素具有良好的去除能力，可为蓝藻资源化提供思路。
Abstract:Using cyanobacteria as raw material to prepare biochar, the adsorption efficiency of cyanobacteria biochar on tetracycline at different temperatures was investigated and the optimal preparation temperature of cyanobacteria biochar was screened. Cyanobacteria biochar modified with different Fe/C mass ratios was prepared by the liquid phase reduction method. The removing efficiency, influencing factors and removing mechanism of the iron-modified cyanobacteria biochar for tetracycline were studied. The results showed that the iron-modified cyanobacteria biochar had a high removing capacity for tetracycline at 700 ℃ and an iron-carbon mass ratio of 1∶1, and the removing rate reached 87.2% in 60 min, which was 1.2 times of that before modification. The adsorption type was in accordance with the pseudo-second-order kinetic equation (R2>0.99). The relationship between the iron-modified cyanobacteria biochar tetracycline removal performance and its structure was discussed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). It was proved that the main removal effects of tetracycline were adsorption and chemical degradation, the zero-valent iron as the electron donor promoted the redox reaction, and the oxygen-containing functional groups as the bridge of electron transfer played an important role in the adsorption and degradation process. The test results of influencing factors showed that the influence degree of anions was in the order of SO4 2− > Cl−, the influence degree of cations was Ca2+ > Na+, and the influence degree of organic fulvic acid (FA) was weak relative to ionic strength. The iron-modified cyanobacteria biochar had good removal efficiency on tetracycline antibiotics, which could provide a new idea for cyanobacteria resource utilization.
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Key words:
- cyanobacteria /
- biochar /
- tetracycline /
- adsorption /
- degradation
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图 1 不同温度下制备的蓝藻生物炭对四环素的吸附量
Figure 1. Tetracycline adsorption capacity of cyanobacteria biochar prepared at different temperatures
图 2 铁改性前后蓝藻生物炭吸附-脱附等温线
Figure 2. Adsorption and desorption isotherms of cyanobacterial biochar before and after iron modification
图 3 Z700、nZVI@Z700、nZVI的SEM及TEM图谱
Figure 3. SEM of Z700, nZVI@Z700 , nZVI and TEM of nZVI@Z700
图 4 铁改性前后蓝藻生物炭XRD图谱
Figure 4. XRD patterns of cyanobacterial biochar before and after iron modification
图 5 不同铁炭比蓝藻生物炭对四环素的去除效果
Figure 5. Tetracycline removal efficiency by cyanobacterial biochar with different iron-carbon ratios
图 6 nZVI@Z700、Z700、nZVI对四环素的去除效果
Figure 6. Removal efficiency of tetracycline by nZVI@Z700, Z700 and nZVI
图 7 nZVI@Z700吸附四环素的拟合曲线
Figure 7. Fitting curve of tetracycline adsorption by nZVI@Z700
图 8 离子及FA浓度对nZVI@Z700去除四环素的影响
Figure 8. Effect of ionic and FA concentration on tetracycline removing by nZVI@Z700
图 9 nZVI@Z700投加量对四环素去除效果的影响
Figure 9. Effect of nZVI@Z700 dosage on tetracycline removal efficiency
图 10 nZVI@Z700及nZVI@Z700吸附四环素后SEM图
Figure 10. SEM of nZVI@Z700 and after absorption of tetracycline
图 11 nZVI@Z700吸附四环素前后红外光谱图
Figure 11. FT-IR of nZVI@Z700 before and after absorption of tetracycline
图 12 nZVI@Z700吸附四环素前后XPS总谱图
Figure 12. XPS spectra of nZVI@Z700 before and after absorption of tetracycline
图 13 nZVI@Z700吸附四环素前后XPS拟合
Figure 13. XPS fitting of nZVI@Z700 before and after absorption of tetracycline
表 1 铁改性前后蓝藻生物炭的孔结构参数
Table 1. Pore structure parameters of cyanobacterial biochar before and after iron modification
样品 孔径/nm 比表面积/（m2/g） 孔容积/（cm3/g） Z700 7.911 0 42.703 2 0.084 5 nZVI@Z700 8.977 7 70.592 0 0.158 4 
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表 2 nZVI@Z700去除四环素动力学参数
Table 2. Kinetic parameters of tetracycline removal by nZVI@Z700
伪一级动力学 伪二级动力学 颗粒内扩散模型 k1/
min−1R2 k2/
〔(mg/(g·min)〕qe
/(mg/g)R2 ki/
〔(mg/(g·min−1/2)〕R2 0.001 1×103 0.687 2 0.001 5×103 104.167 0 0.999 8 0.605 0 0.569 7
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